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EP2631974B2 - Batterie au lithium - Google Patents
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EP2631974B2 - Batterie au lithium - Google Patents

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Publication number
EP2631974B2
EP2631974B2 EP12179388.9A EP12179388A EP2631974B2 EP 2631974 B2 EP2631974 B2 EP 2631974B2 EP 12179388 A EP12179388 A EP 12179388A EP 2631974 B2 EP2631974 B2 EP 2631974B2
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EP
European Patent Office
Prior art keywords
aqueous binder
lithium battery
material layer
active material
unit
Prior art date
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Application number
EP12179388.9A
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German (de)
English (en)
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EP2631974A1 (fr
EP2631974B1 (fr
Inventor
In-Seop Byun
Young-Bae Sohn
Kyeong-Min Jeong
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a lithium battery.
  • lithium batteries To comply with demand for small and high-performance devices, it is important to manufacture small and light-weight lithium batteries. Also, for use in electric vehicles, discharging capacity, energy density, and cycle characteristics of lithium batteries are taken into consideration as important factors. For use in such appliances, lithium batteries with large discharge capacity, high energy density per unit volume, and excellent lifespan characteristics are required.
  • a separator is included in a lithium battery to prevent short-circuiting between a positive electrode and a negative electrode.
  • An organic-based separator melts at a temperature of 200°C or less. Accordingly, when the temperature of a battery including an organic-based separator is increased due to inner and/or external stimuli, a volumetric change may occur due to shrinking or melting of the separator, and thus, the operation of a battery is stopped.
  • a typical separator has low adhesion with an electrode. Accordingly, during charging and discharging, the distance between electrodes may increase, and thus, the degree of expansion is substantially increased. Due to the increase in the volume of the battery, the capacity and energy density per unit volume may be reduced. Substantial volumetric change of a battery may lead to destruction of the separator. Accordingly, lifespan characteristics of a lithium battery including a separator may be decreased.
  • EP 0991132 discloses a nonaqueous electrolyte secondary battery including an electrode group comprising a positive electrode, a negative electrode, and a separator, a jacket for housing the electrode group, and a nonaqueous electrolyte with which the electrode group is impregnated.
  • EP 1261048 discloses a method for producing electrodes for electrochemical element which contain at least one lithium-intercalating electrode.
  • WO99/09604 discloses a method of stabilizing a polymeric film of an electrochemical cell, said polymeric film comprising: a copolymer of vinylidene fluoride and at least one other fluorinated monomer.
  • a lithium battery is provided as defined in the claims.
  • a lithium battery according to the invention may have improved adhesion between the separator and an electrode.
  • a separator having at least a surface on which a polymer layer including a non-aqueous binder is formed, and a negative electrode comprising a negative active material layer including two or more aqueous binders, adhesion between the separator and the electrode may be improved and thus, a formed lithium battery may have improved lifespan characteristics.
  • a lithium battery according to the present invention includes a positive electrode, a negative electrode, and a separator, wherein the separator includes a base material layer and a polymer layer formed on at least one surface of the base material layer, the polymer layer includes a non-aqueous binder, the negative electrode includes a first aqueous binder and at least one second aqueous binder, and the first aqueous binder includes the same monomer unit as in the non-aqueous binder.
  • the negative electrode including an aqueous binder that has the same monomer unit as in the non-aqueous binder of the polymer layer, adhesion between the negative electrode and the separator is improved and thus, resistance of an electrode plate is reduced and charging and discharging characteristics of a lithium battery may be improved, and also, volumetric change of a lithium battery during charging and discharging may be suppressed.
  • the negative electrode includes at least one second aqueous binder, adhesion between the negative active material layer and a current collector, e.g. copper foil, may be improved.
  • the negative electrode included in the lithium battery is manufactured by using water instead of an organic solvent, the manufacturing process is simple and environmentally friendly, and the manufacturing costs are low.
  • the first aqueous binder of the negative electrode of the lithium battery may include at least one selected from the group consisting of a diene-based monomer unit, an acryl-based monomer unit, a fluorine-based monomer unit, and a silicon-based monomer unit.
  • the first aqueous binder may be either in an aqueous dispersion form in which a polymer including the monomer unit is dispersed in water or in an aqueous solution form in which a polymer is dissolved in water, but is not limited to these forms and any of various forms that are available in the art may be used herein.
  • the first aqueous binder may include at least one selected from the group consisting of a butadiene unit, an isoprene unit, an acrylate ester unit, a methacrylate ester unit, a vinylidenefluoride unit, a tetrafluoroethylene unit, a hexafluoropropylene unit, and a siloxane unit.
  • the first aqueous binder may comprise a copolymer.
  • the first aqueous binder may include a copolymer of a vinylidenefluoride-based monomer and at least one monomer selected from the group consisting of tetrafluoroethylene and hexafluoropropylene.
  • the copolymer may additionally include an olefin-based monomer.
  • the olefin-based monomer included in the copolymer may include at least one selected from the group consisting of ethylene, propylene, butene, butadiene, isoprene, and pentene, but is not limited thereto and any of various olefin-based monomers that are available in the art may be used herein.
  • the copolymer may additionally include a hydrophilic group selected from the group consisting of a carboxylic acid group, a hydroxyl group, and a sulfonic acid group, but the hydrophilic group is not limited thereto and any of various hydrophilic groups that are available in the art may be used herein.
  • the copolymer may include a cationic hydrophilic group, a non-ionic hydrophilic group, and/or an amphoteric hydrophilic group. Due to the additional inclusion of the hydrophilic group in the copolymer, water dispersion properties may be further enhanced.
  • the amount of the hydrophilic group included in the copolymer is the amount of a monomer including the hydrophilic group during polymerization, and may be in the range of 0.1 to 40 wt% based on the total weight of the monomer.
  • the amount of the hydrophilic group may be in a range of 0.5 to 20 wt%. Within this amount range, dispersibility of the copolymer may be further increased.
  • the second aqueous binder may include at least one selected from the group consisting of styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, acryl rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyethylene, polypropylene, ethylenepropylene copolymer, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, ethylenepropylenediene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, a polyester resin, an acryl resin, a phenol resin, an epoxy resin, polyvinylalcohol, hydropropylmethylcellulose, hydroxypropylcellulose, and diacetylcellulose, but is not limited thereto and any of
  • the first aqueous binder and the second aqueous binder included in the lithium battery are mixed at a weight ratio of 0.1:1 to 10:1.
  • the first aqueous binder and the second aqueous binder may be mixed at a weight ratio of 0.1:1 to 2:1.
  • the first aqueous binder and the second aqueous binder may be mixed at a weight ratio of 0.1:1 to 1:1.
  • the weight ratio is less than 0.1:1, the adhesion force may be decreased.
  • the adhesion force between a separator and an active material layer is weak and thus, they may be separated from each other.
  • the weight ratio is greater than 10:1
  • the energy density of a battery may be reduced and the adhesion force with the separator may be reduced.
  • the adhesion force between a negative electrode substrate and an active material layer may be weak and thus, they may be separated from each other.
  • the amount of the first aqueous binder included in the negative active material layer in the lithium battery may be, based on a total amount of a negative active material layer, in the range of 0.01 wt% to 10 wt%.
  • the amount of the first aqueous binder may be in the range of 0.01 wt% to 5 wt% based on the total amount of the negative active material layer.
  • the amount of the first aqueous binder may be in the range of 0.05 wt% to 5 wt% based on the total amount of the negative active material layer.
  • the amount of the first aqueous binder may be in the range of 0.01 wt% to 3 wt% based on the total amount of the negative active material layer.
  • the amount of the first aqueous binder may be in the range of 0.01 wt% to 1 wt% based on the total amount of the negative active material layer.
  • the amount of the first aqueous binder is less than 0.01 wt%, the adhesion force with respect to the separator may be reduced, and when the amount of the first aqueous binder is greater than 10 wt%, the energy density of a battery may be reduced.
  • the separator included in the lithium battery may include, for example, as illustrated in FIG. 1 , a base material layer 11 and polymer layers 12 and 13 formed on surfaces of the base material layer.
  • the polymer layer includes a non-aqueous binder having a same monomer structure as that in the first aqueous binder included in the negative electrode. Thus, adhesion of the separator with the negative electrode may be enhanced.
  • the non-aqueous binder included in the polymer layer may include at least one selected from the group consisting of polyethylene, polypropylene, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluorine, polytetrafluoroethylene, polyvinyl acetate, polyvinylalcohol, polyvinylisobutylether, polyacrylonitrile, polymethacrylonitrile, methyl polymethacrylate, methyl polyacrylate, ethyl polymethacrylate, allyl acetate, polystyrene, polybutadiene, polyisoprene, polyoxymethylene, polyoxyethylene, polycyclothioether, polydimethylsiloxane, polylactone, polyethyleneterephthalate, polycarbonate, nylon 6, nylon 66, poly-m-phenyleneisophthalamide, poly-p-phenyleneterephthalamide, and polypyromellitimide, but is not limited there
  • the thickness of the polymer layer of the separator may be in the range of 0.1 ⁇ m to 10 ⁇ m.
  • the thickness of the polymer layer may be in the range of 0.5 ⁇ m to 8 ⁇ m.
  • the base material layer of the separator may be an organic layer.
  • the base material layer may be a porous film that does not have electron conductivity, has ionic conductivity, has high durability with respect to an organic solvent, and has fine pore diameters.
  • the thickness of the base material layer may be, for example, in the range of 0.5 to 40 ⁇ m, or 1 to 30 ⁇ m, or 1 to 10 ⁇ m. When the base material layer has such thickness ranges, separator-induced resistance of a battery may be reduced and also, during coating on the separator, workability may be improved.
  • the base material layer of the separator may be a porous film including a polyolefin.
  • Polyolefin has excellent short-circuiting prevention effects and also, may improve stability of a battery due to a shut-down effect.
  • the base material layer may be a porous film that includes a polyolefin, such as polyethylene, polypropylene, polybutene, or polyvinyl chloride, or a combination or copolymer thereof, but is not limited thereto and any of various porous films that are available in the art may be used herein.
  • a porous film that consists of a resin, such as polyethyleneterephthalate, polycycloolefin, polyethersulfone, polyamide, polyimide, polyimideamide, polyaramide, polycycloolefin, nylon, polytetrafluoroethylene, or the like; a porous film formed by weaving polyolefin-based fiber; a non-woven fabric including polyolefin; an assembly of insulating material particles; or the like may be used.
  • a resin such as polyethyleneterephthalate, polycycloolefin, polyethersulfone, polyamide, polyimide, polyimideamide, polyaramide, polycycloolefin, nylon, polytetrafluoroethylene, or the like
  • a porous film formed by weaving polyolefin-based fiber such as polyethyleneterephthalate, polycycloolefin, polyethersulfone, polyamide, polyimide, polyimideamide, polyaramide, polycycloolefin
  • a porous film including a polyolefin may allow a polymer slurry for preparing the polymer layer formed on the base material layer to have excellent coating properties and may enable the preparation of a thin separator film to increase the ratio of an active material in a battery and the capacity per volume.
  • the polyolefin used as the material for forming the base material layer may be a homopolymer, a copolymer, or a mixture of polyethylene, polypropylene, or the like.
  • Polyethylene may be low-density, middle-density, or high-density polyethylene, and in consideration of mechanical strength, high-density polyethylene may be used.
  • two or more kinds of polyethylene may be used to provide flexibility.
  • the polymerization catalyst that is used in preparing polyethylene may not be limited, and a Ziegler-Natta based catalyst, or a Philips-based catalyst, or a metallocene catalyst, or the like may be used.
  • the weight average molecular amount of polyethylene may be in the range of 0.1 million to 12 million, for example, 0.2 million to 3 million.
  • the polypropylene may be a homopolymer, a random copolymer, a block copolymer, or a combination thereof.
  • the polymerization catalyst may not be limited, and a Ziegler-Natta based catalyst, a metallocene catalyst, or the like may be used as the polymerization catalyst.
  • tacticity is not limited, and isotactic, syndiotactic, or atactic may be used, and for example, relatively inexpensive isotactic polypropylene may be used.
  • polyolefins other than polyethylene and polypropylene an antioxidant, or the like may be further used.
  • the negative electrode of the lithium battery may include a carbonaceous negative active material.
  • the carbonaceous negative active material may be crystalline carbon, non-crystalline carbon, or a mixture thereof.
  • the crystalline carbon may be natural or artificial graphite in an amorphous, tabular, flake-like, spherical, or fibrous form, and the non-crystalline carbon may be soft carbon (low temperature calcined carbon), hard carbon, mesophase pitch carbide, calcined corks, or the like, but is not limited thereto, and any of various carbonaceous negative active materials that are available in the art may be used herein.
  • the positive electrode of the lithium battery may include the same non-aqueous binder as in the polymer layer of the separator. Due to the inclusion of the same non-aqueous binder of the positive electrode and the separator, adhesion between the positive electrode and the separator may be improved.
  • the positive electrode of the lithium battery may include the same aqueous binder as in the negative electrode. Due to the inclusion of an aqueous binder that includes the same monomer unit as in the separator, adhesion between the positive electrode and the separator may be improved.
  • the lithium battery may be manufactured by using the following method.
  • the positive electrode is prepared.
  • a positive active material, a conductive material, a binder, and a solvent are mixed to prepare a positive active material composition.
  • the positive active material composition is directly coated on a metal current collector to prepare a positive electrode plate.
  • the positive active material composition can be cast on a separate support, and then a film separated from the support is laminated on a metal current collector to complete the preparation of a positive electrode plate.
  • the positive electrode may also be manufactured by using other methods.
  • any one of various lithium-containing metal oxides that are known in the art may be used herein without limitation.
  • at least one of a composite oxide including lithium and metal selected from cobalt, manganese, nickel, and a combination thereof may be used.
  • Li a A 1-b B b D 2 (where 0.90 ⁇ a ⁇ 1.8, and 0 ⁇ b ⁇ 0.5); Li a E 1-b B b O 2-c D c (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b B b O 4-c D c (where 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); Li a Ni 1-b-c Co b B c D ⁇ (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ ⁇ ⁇ 2); Li a Ni 1-b-c Co b B c O 2- ⁇ F ⁇ , (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05,
  • A is Ni, Co, Mn, or a combination thereof
  • B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare-earth element or a combination thereof
  • D is O, F, S, P, or a combination thereof
  • E is Co, Mn, or a combination thereof
  • F is F, S, P, or a combination thereof
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof
  • Q is Ti, Mo, Mn, or a combination thereof
  • I is Cr, V, Fe, Sc, Y, or a combination thereof
  • J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • these compounds may have a coating layer on their surfaces, or these compounds may be mixed with a compound including a coating layer.
  • the coating layer may include a coating element compound, such as an oxide or hydroxide of a coating element, an oxyhydroxide of a coating element, oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • These compounds that constitute the coating layers may be non-crystalline or crystalline.
  • a coating element included in a coating layer Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof may be used.
  • a process for forming a coating layer may be any one of various coating methods (for example, spray coating, immersion, or the like) that use these compounds and these elements and do not adversely affect physical properties of the positive active material. These coating methods are known to one of ordinary skill in the art and thus, are not described in detail herein.
  • the conductive material may be carbon black or graphite particles, but is not limited thereto, and any one of various conductive materials that are available in the art may be used herein.
  • binder examples include a vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidenefluoride(PVDF), polyacrylonitrile, polymethylmetacrylate, polytetrafluoroethylene, and a mixture thereof, and a styrene butadiene rubber-based polymer, but are not limited thereto, and any one of various binders that are available in the art may be used herein.
  • PVDF polyvinylidenefluoride
  • the same non-aqueous binder as in the polymer layer of the separator may be used, or the same aqueous binder as in the negative electrode may be used.
  • solvent examples include N-methylpyrrolidone, acetone, and water, but are not limited thereto, and any one of various materials that are known in the art may be used herein.
  • Amounts of the positive active material, the conductive material, the binder, and the solvent may be at the same levels used in a typical lithium battery. According to the purpose or structure of a lithium battery, at least one of the conductive material, the binder, and the solvent may be omitted.
  • the negative electrode is prepared.
  • a negative active material, a conductive material, two or more aqueous binders, and a solvent are mixed to prepare a negative active material composition.
  • the negative active material composition is directly coated and dried on a metal current collector to prepare a negative electrode plate.
  • the negative active material composition may be cast on a separate support, and then a film separated from the support is laminated on a metal current collector to complete the preparation of a negative electrode plate.
  • the negative active material may be a carbonaceous material as described above, but is not limited thereto, and any one of various materials that are used as a negative active material for a lithium battery is used herein.
  • the negative active material may include at least one selected from the group consisting of lithium metal, a metal that is alloyable with lithium, a transition metal oxide, a non-transition metal oxide, and a carbonaceous material.
  • the metal that is alloyable with lithium may be Si, Sn, Al, Ge, Pb, Bi, Sb, an Si-Y alloy (where Y is alkali metal, alkali earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare-earth element, or a combination thereof and is not Si), an Sn-Y alloy (the Y is alkali metal, alkali earth metal, a Group 13 element, a Group 14 element, transition metal, a rare-earth element, or a combination thereof and is not Sn), or the like.
  • Si-Y alloy where Y is alkali metal, alkali earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare-earth element, or a combination thereof and is not Si
  • Sn-Y alloy the Y is alkali metal, alkali earth metal, a Group 13 element, a Group 14 element, transition metal, a rare-earth element, or a combination thereof and is not Sn
  • the element Y may be Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
  • the transition metal oxide may be a lithium titanium oxide, a vanadium oxide, a lithium vanadium oxide, or the like.
  • the non-transition metal oxide may be SnO 2 , SiO x (0 ⁇ x ⁇ 2), or the like.
  • the conductive material used in the negative active material composition may be the same as that in the positive active material composition.
  • the binder includes two or more aqueous binders as described above and the solvent is water.
  • a plasticizer may be further added to the positive active material composition and/or negative active material composition to form pores inside an electrode plate.
  • Amounts of the negative active material, the conductive material, the binder, and the solvent may be may be at the same levels used in a typical lithium battery.
  • At least one of the conductive material, the binder, and the solvent may be omitted.
  • the separator is prepared.
  • the separator as described above, includes a base material layer and a polymer layer disposed on one or two surfaces of the base material layer.
  • the base material layer may be formed by using publicly known and available methods.
  • the base material layer may be formed by using a dry method as follows: polypropylene and polyethylene are molten and extruded to form a film, followed by annealing at low temperature and growing a crystal domain, and in this state, elongation is performed thereon to extend a non-crystalline region to form a microporous film.
  • the base material layer may be formed by using a wet method as follows: small molecular materials, such as a hydrocarbon solvent, are mixed with polypropylene and polyethylene to form a film, and subsequently, a non-crystalline island phase is formed within the film by gathering of a solvent or small molecules, and then the island phase is removed by extracting the solvent and small molecules with other volatile solvents to form a microporous film.
  • small molecular materials such as a hydrocarbon solvent
  • the base material layer may include non-conductive particles, other different fillers, a fiber compound, or the like.
  • the base material layer may be surface-treated with a small molecular compound or a polymer compound, it may be treated with an electronic ray, such as an ultraviolet ray, or it may be subjected to plasma treatment using a corona discharge plasma gas.
  • a polymer compound including a polar group such as a carboxylic acid group, a hydroxyl group, a sulfonic acid group, or the like, may be treated on the base material layer because the polymer compound has high impregnation properties of an electrolytic solution and high adhesion with a porous film including non-conductive particles and a binder.
  • the base material layer may have a multi-layer structure including at least one base material layer.
  • the base material layer may be a stack including a polyethylene microporous film and a polypropylene microporous film, a stack including a non-woven fabric and a polyolefin-based separator, or the like.
  • the polymer layer formed on one or two surfaces of the base material layer may be a porous film including a non-aqueous binder.
  • the porous film structure of the polymer layer may provide excellent impregnation properties of an electrolytic solution and high ion permeation properties.
  • the polymer layer may be formed by using publicly known and available methods. For example, a slurry including a non-aqueous binder and NMP is prepared and then, the slurry is coated on the base material layer and then, the resultant was passed through a bath including a solvent that is a non solvent or poor solvent with respect to the non-aqueous binder and has affinity to NMP so as to allow phase change to occur, followed by drying to form a porous polymer layer.
  • a slurry including a non-aqueous binder and NMP is prepared and then, the slurry is coated on the base material layer and then, the resultant was passed through a bath including a solvent that is a non solvent or poor solvent with respect to the non-aqueous binder and has affinity to NMP so as to allow phase change to occur, followed by drying to form a porous polymer layer.
  • a polymer layer is formed by rapid organic phase separation of the non-solvent or poor solvent, and resin backbones are connected to each other to form a fine three-dimensional porous structure. That is, by contacting a solution in which a non-aqueous binder is dissolved with a solvent that is a non-solvent or poor solvent with respect to the non-aqueous binder and has affinity for NMP that is used to dissolve or disperse the non-aqueous binder, high-speed phase separation may occur and accordingly, the polymer layer may have a 3-dimensional porous mesh structure.
  • the polymer layer may include inorganic particles. Due to the inclusion of the inorganic particles, the separator may have improved antioxidant properties and deterioration of characteristics of a battery may be suppressed.
  • the inorganic particles may include alumina (Al 2 O 3 ), silica (SiO 2 ), titania (TiO 2 ), or the like.
  • the average particle size of the inorganic particles may be in the range of 10 nm to 5 ⁇ m.
  • the average particle size of the inorganic particles is less than 10 nm, crystallinity of the inorganic particles may be degraded and thus the effects of the particles may be negligible; and when the average particle size of the inorganic particles is greater than 5 ⁇ m, it is difficult to disperse inorganic particles.
  • the electrolyte may be in a liquid or gel state.
  • the electrolyte may be an organic electrolytic solution.
  • the electrolyte may be solid.
  • the solid electrolyte may be a boron oxide, lithium oxynitride, or the like, but is not limited thereto, and any one of various materials that are used as a solid electrolyte in the art may be used herein.
  • the solid electrolyte may be formed on the negative electrode by, for example, sputtering.
  • an organic electrolytic solution is prepared.
  • An organic electrolytic solution may be prepared by dissolving a lithium salt in an organic solvent.
  • the organic solvent may be any one of various organic solvents that are available in the art.
  • the organic solvent may be propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofurane, ⁇ -butyrolactone, dioxolane, 4-methyldioiorane, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethylcarbonate, methylisopropylcarbonate, ethylpropylcarbonate, dipropylcarbonate, dibutylcarbonate, diethyleneglycol, dimethylether, a mixture thereof, or the
  • the lithium salt may be any one of various lithium salts that are available in the art.
  • the lithium salt may be LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO2)(CyF 2y+1 SO 2 ) (where x and y are natural numbers), LiCl, LiI, a mixture thereof, or the like.
  • a lithium battery 1 includes a positive electrode 3, a negative electrode 2, and a separator 4.
  • the positive electrode 3, the negative electrode 2, and the separator 4 are wound or folded to be placed in a battery case 5. Then, an organic electrolytic solution is injected to the battery case 5, followed by sealing with a cap assembly 6, thereby completing the manufacture of the lithium battery 1.
  • the battery case 5 may be cylindrical or rectangular, or may have a thin-film shape.
  • the lithium battery 1 may be a thin film battery.
  • the lithium battery 1 may be a lithium ion battery.
  • the separator may be placed between the positive electrode and the negative electrode to form a battery assembly.
  • a plurality of battery assemblies may be stacked in a bi-cell structure, and impregnated with an organic electrolytic solution, and the obtained result is housed in a pouch and sealed, thereby completing the manufacture of a lithium ion polymer battery.
  • a plurality of battery assemblies may be stacked to form a battery pack, and the battery pack can be used in devices requiring high capacity and high power output.
  • the battery pack may be used in a notebook computer, a smartphone, an electric vehicle (EV), or the like.
  • olefin-based vinylidenefluoride-hexafluoropropylene copolymer 0.25 parts by weight of an olefin-based vinylidenefluoride-hexafluoropropylene copolymer as a first aqueous binder, 1 part by weight of styrene-butadiene rubber (SBR) as a second aqueous binder, 1 part by weight of carboxymethylcellulose (CMC) as a thickener, and 97.75 parts by weight of graphite particles (MAG-4V, Japan Chemistry) having an average particle size of 25 ⁇ m were mixed to prepare 100 parts by weight of a mixed material of an active material and a binder.
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • a carbonaceous conductive material (SFG6, Timcal Inc.) were mixed with the mixed material, followed by stirring using a mechanical stirrer for 60 minutes to prepare a slurry.
  • the slurry was coated to a thickness of about 60 ⁇ m on a copper current collector having a thickness of about 15 ⁇ m by using a doctor blade, dried in a hot air stream drier at a temperature of 100°C for 2 hours and dried at a temperature of 120°C for 2 hours to complete the preparation of a negative electrode plate.
  • a negative electrode was prepared in the same manner as in Preparation Example 1, except that the amount of the first aqueous binder was 0.5 parts by weight and the amount of the graphite particles was 97.5 parts by weight.
  • a negative electrode was prepared in the same manner as in Preparation Example 1, except that the amount of the first aqueous binder was 1.0 parts by weight and the amount of the graphite particles was 97.0 parts by weight.
  • a negative electrode was prepared in the same manner as in Preparation Example 1, except that the amount of the first aqueous binder was 2.0 parts by weight and the amount of the graphite particles was 96.0 parts by weight.
  • a negative electrode was prepared in the same manner as in Preparation Example 1, except that the amount of the first aqueous binder was 5.0 parts by weight and the amount of the graphite particles was 93.0 parts by weight.
  • a negative electrode was prepared in the same manner as in Preparation Example 1, except that 3 parts by weight of an olefin-based vinylidenefluoride-hexafluoropropylene copolymer was used as the first aqueous binder, a second aqueous binder was not used, 1 part by weight of carboxymethylcellulose (CMC) was used as a thickener, and the amount of graphite particles was 96.0 parts by weight.
  • CMC carboxymethylcellulose
  • a negative electrode was prepared in the same manner as in Preparation Example 1, except that 1 part by weight of styrene-butadiene rubber (SBR) was used as the second aqueous binder, 1 part by weight of carboxymethylcellulose (CMC) was used as a thickener, a first aqueous binder was not used, and the amount of graphite particles was 98.0 parts by weight.
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • PVDF polyvinylidenefluoride
  • N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone
  • the porous film on which the coating layers were formed was placed in a bath and then phase change was performed thereon, followed by drying with a hot air stream, thereby completing the preparation of a separator including a base material layer having surfaces on which a PVDF polymer layer was formed.
  • a coin cell was manufactured by using the negative electrode plate prepared according to Preparation Example 1, lithium metal as a reference electrode, the separator prepared according to Preparation Example 6, and an electrolyte prepared by dissolving 1.3M LiPF 6 in a mixed solution including ethylene carbonate (EC): ethylmethyl carbonate (EMC): diethyl carbonate (DEC) at a volumetric ratio of 3:5:2.
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • DEC diethyl carbonate
  • a lithium battery was manufactured in the same manner as in Example 1, except that the negative electrode plate prepared according to Preparation Example 2 was used.
  • a lithium battery was manufactured in the same manner as in Example 1, except that the negative electrode plate prepared according to Preparation Example 3 was used.
  • a lithium battery was manufactured in the same manner as in Example 1, except that the negative electrode plate prepared according to Preparation Example 4 was used.
  • a lithium battery was manufactured in the same manner as in Example 1, except that the negative electrode plate prepared according to Preparation Example 5 was used.
  • a lithium battery was manufactured in the same manner as in Example 1, except that the negative electrode plate prepared according to Comparative Preparation Example 1 was used.
  • a lithium battery was manufactured in the same manner as in Example 1, except that the negative electrode plate prepared according to Comparative Preparation Example 2 was used.
  • the adhesion force was evaluated through a 180° peel test to measure the adhesion force between a negative electrode material layer and a copper substrate.
  • a pressed negative electrode plate was attached to a slide glass by using double-sided tape and a force applied to detach the copper substrate at an angle of 180 degrees was measured by using an adhesion force measuring device.
  • the pressing was performed at a temperature of 100°C with a pressure of 250 kg for 180 seconds.
  • the substrate adhesion force of the negative electrode of Comparative Preparation Example 2 was assumed to be 100 and relative substrate adhesion forces of the negative electrodes of Preparation Examples 1-5 and Comparative Preparation Example 1 are shown in Table 1 below.
  • Table 1 Substrate adhesion force before impregnation with electrolytic solution Preparation Example 1 400
  • Preparation Example 2 550 Preparation Example 3
  • Preparation Example 4 800 Preparation Example 5 1000 Comparative Preparation Example 1 250 Comparative Preparation Example 2 100
  • the negative electrode plates prepared according to Preparation Examples 1 to 5 and Comparative Preparation Examples 1 to 2 and the separator prepared according to Preparation Example 6 were pressed to manufacture assemblies, and then the assemblies were impregnated with the electrolytic solution used in Example 1 and adhesion forces thereof were evaluated as in Evaluation Example 1.
  • the pressing was performed at a temperature of 100°C with a pressure of 250 kg for 180 seconds.
  • the substrate adhesion force of the negative electrode of Comparative Preparation Example 2 was assumed to be 100 and relative adhesion forces of the negative electrodes of Preparation Examples 1-5 and Comparative Preparation Example 1 are shown in Table 2 below.
  • Table 2 Substrate adhesion force after impregnation with electrolytic solution Preparation Example 1 182
  • Preparation Example 2 214
  • Preparation Example 3 270
  • Preparation Example 4 400
  • Preparation Example 5 Comparative Preparation Example 1 170 Comparative Preparation Example 2 100
  • a battery manufactured using a negative electrode plate according to the Preparation Examples is more suitable for suppression of volumetric change of a battery during charging and discharging than a battery manufactured using a negative electrode plate according to the Comparative Preparation Examples.
  • the electrode plate resistance of the negative electrode plates of Preparation Examples 1 to 5 and Comparative Preparation Examples 1 to 2 was measured.
  • a resistance between two spots on a surface of an electrode plate was measured by using a resistance measuring device (ohmmeter).
  • the coin cells manufactured according to Examples 1 to 5 and Comparative Examples 1 to 2 were charged and discharged once with a constant current of 0.1C rate in a voltage range of 0.01 to 1.5 V with respect to a lithium metal at a temperature of 25°C (a formation step).
  • the initial charging and discharging efficiency is obtained by dividing a discharging capacity by a charging capacity in a first cycle in the formation step and then multiplying the result by 100.
  • Table 4 Initial charging and discharging efficiency in formation step [%] Discharging capacity in formation step [mAh/g] Discharging capacity in standard charging and discharging step [mAh/g]
  • Example 1 94.5 364 367
  • Example 2 94.6 370 370
  • Example 3 94.7 367 367
  • Example 4 94.8 365 365
  • Example 5 94.7 364 366 Comparative Example 1 93.9 364 366 Comparative Example 2 94.5 361 364
  • a lithium battery according to the Examples has higher initial charging and discharging efficiency and discharging capacity than a lithium battery of the Comparative Examples.
  • the lithium batteries of Examples 1 to 5 showed high-rate characteristics and lifespan characteristics similar to the lithium batteries of Comparative Examples 1 to 2.

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Claims (14)

  1. Batterie au lithium comprenant :
    une électrode positive comprenant une couche de matière active positive ;
    une électrode négative comprenant une couche de matière active négative ; et
    un séparateur comprenant une couche de matière de base et une couche de polymère incluant un liant non aqueux formé sur au moins une surface de la couche de matière de base ;
    dans laquelle la couche de matière active négative comprend un premier liant aqueux et au moins un second liant aqueux, le premier liant aqueux comprenant le même motif monomère que celui du liant non aqueux ; dans laquelle le premier liant aqueux et le second liant aqueux sont inclus dans la couche de matière active négative selon un rapport en poids de 0,1:1 à 10:1.
  2. Batterie au lithium selon la revendication 1, dans laquelle le premier liant aqueux comprend au moins un motif monomère choisi dans le groupe constitué en un motif monomère diénique, un motif monomère acrylique, un motif monomère fluoré et un motif à base de silicium.
  3. Batterie au lithium selon la revendication 1 ou 2, dans laquelle le premier liant aqueux comprend au moins un motif monomère choisi dans le groupe constitué en un motif butadiène, un motif isoprène, un motif ester d'acrylate, un motif ester de méthacrylate, un motif fluorure de vinylidène, un motif tétrafluoréthylène, un motif hexafluoropropylène et un motif siloxane.
  4. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle le premier liant aqueux comprend un copolymère d'un monomère à base de fluorure de vinylidène et d'au moins un monomère choisi dans le groupe constitué en le tétrafluoréthylène et l'hexafluoropropylène.
  5. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle le premier liant aqueux comprend un copolymère qui comprend un monomère oléfinique.
  6. Batterie au lithium selon la revendication 4 ou la revendication 5, dans laquelle le copolymère comprend un groupe hydrophile choisi dans le groupe constitué en un groupe acide carboxylique, un groupe hydroxyle et un groupe acide sulfonique.
  7. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle le second liant aqueux comprend au moins un élément choisi dans le groupe constitué en un caoutchouc styrène-butadiène, un caoutchouc styrène-butadiène acrylé, un caoutchouc acrylonitrile-butadiène, un caoutchouc acrylonitrile-butadiène-styrène, un caoutchouc acrylique, un caoutchouc butylique, un caoutchouc fluoré, un polytétrafluoréthylène, un polyéthylène, un polypropylène, un copolymère d'éthylène-propylène, un oxyde de polyéthylène, une polyvinylpyrrolidone, une polyépichlorhydrine, un polyphosphazène, un polyacrylonitrile, un polystyrène, un copolymère d'éthylène-propylène-diène, une polyvinylpyridine, un polyéthylène chlorosulfoné, un latex, une résine de polyester, une résine acrylique, une résine phénolique, une résine époxy, un alcool polyvinylique, l'hydropropyl-méthylcellulose, l'hydroxypropylcellulose et la diacétylcellulose.
  8. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle le premier liant aqueux est inclus dans la couche de matière active négative dans une plage de 0,01 % en poids à 10 % en poids par rapport au poids total de la couche de matière active négative.
  9. Batterie au lithium selon la revendication 8, dans laquelle le premier liant aqueux est inclus dans la couche de matière active négative dans une plage de 0,05 % en poids à 5 % en poids par rapport au poids total de la couche de matière active négative.
  10. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle le liant non aqueux comprend au moins un élément choisi dans le groupe constitué en un polyéthylène, un polypropylène, un polyisobutylène, un chlorure de polyvinyle, un chlorure de polyvinylidène, un fluorure de polyvinylidène, un polytétrafluoréthylène, un acétate de polyvinyle, un alcool polyvinylique, un éther polyvinylisobutylique, un polyacrylonitrile, un polyméthacrylonitrile, un polyméthacrylate de méthyle, un polyacrylate de méthyle, un polyméthacrylate d'éthyle, un acétate d'allyle, un polystyrène, un polybutadiène, un polyisoprène, un polyoxyméthylène, un polyoxyéthylène, un polycyclothioéther, un polydiméthylsiloxane, une polylactone, un téréphtalate de polyéthylène, un polycarbonate, le Nylon 6, le Nylon 66, un poly-m-phénylèneisophtalamide, un poly-p-phénylène-téréphtalamide et un polypyromellitimide.
  11. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle la couche de matière de base est un film poreux comprenant une polyoléfine.
  12. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle l'épaisseur de la couche de polymère du séparateur est comprise dans la plage allant de 0,1 µm à 10 µm.
  13. Batterie au lithium selon l'une quelconque des revendications précédentes, dans laquelle la couche de matière active positive comprend le même liant non aqueux que celui de la couche de polymère du séparateur.
  14. Batterie au lithium selon l'une quelconque des revendications 1 à 12, dans laquelle la couche de matière active positive comprend le même liant aqueux que le premier liant aqueux de la couche de matière active négative.
EP12179388.9A 2012-02-21 2012-08-06 Batterie au lithium Active EP2631974B2 (fr)

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WO2015102139A1 (fr) * 2014-01-06 2015-07-09 주식회사 엘지화학 Électrode négative pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci
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CN103259039A (zh) 2013-08-21
KR20130096138A (ko) 2013-08-29
EP2631974A1 (fr) 2013-08-28
US20130216891A1 (en) 2013-08-22
EP2631974B1 (fr) 2016-07-27
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